Ab initio study of the effects of

pressure and strain on electronphonon

coupling in IV and IIIV semiconductors
,1

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basic solid state physics

Jelena Sjakste* , Nathalie Vast , Hariom Jani , Sergey Obukhov , and Valeriy Tyuterev
1

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Phys. Status Solidi B 250, No. 4, 716720 (2013) / DOI 10.1002/pssb.201200526

Ecole Polytechnique, Laboratoire des Solides Irradies, CEA-DSM-IRAMIS, CNRS UMR 7642, 91120 Palaiseau, France
Tomsk State Pedagogical University, Tomsk, Russia

Received 24 July 2012, accepted 19 October 2012

Published online 11 April 2013
Keywords density functional theory, intervalley scattering, transport
* Corresponding

author: e-mail jelena.sjakste@polytechnique.edu, Phone: 33 169334511, Fax: 33 169334554

In this work, we examine the pressure and biaxial tensile strain

dependence of the intervalley electronphonon matrix elements
in the lowest conduction band of GaAs, GaP, Si and Ge within
the density functional perturbation theory. We study both
individual transitions and average deformation potential values
which can be used as parameters in transport simulations. In the
case of a hydrostatic pressure, we draw the general conclusion

that the hydrostatic pressure dependence of the intervalley

electronphonon matrix elements can be safely neglected in the
interpretation of most commonly studied phenomena. In
contrast, the case of a biaxial strain in silicon shows that
strain-dependence should be taken into account in calculations
of the intervalley electronphonon matrix elements.

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Electron scattering by phonons is one

of the major processes which determine the transport
characteristics in semiconductors and semiconductor-based
electronic devices [1]. In many cases, the electronphonon
coupling also determines the magnitude of the lifetimes of
electronic states inside the band gap, and the width of the
corresponding absorption peaks, as for example in the case of
direct excitons in GaP, GaAs and Ge [24], or in the case
of shallow impurity states in Si [5, 6]. Despite its great
importance, the electronphonon coupling in semiconductors is still not well understood. The reason is that
experimentally, it is very difficult to access to the electron
phonon scattering strength. Graphene and graphite are quite
unique systems in which the actual value of the electron
phonon coupling constant for some of the phonons can be
obtained almost directly from measurements [7]. When
transport experiments are performed in other materials,
along with electronphonon scattering, many other scattering mechanisms are present at the same time, described by
models involving several ad hoc or adjustable parameters
[8]. A more direct access to the electronphonon coupling
strength is given by spectroscopy experiments in very pure
crystals under a hydrostatic pressure. In several cases, for
GaAs and Ge for example, it was proved that the pressure-

dependence of the broadening of the direct exciton line is

due to electronphonon intervalley scattering [3, 4]. The
effective intervalley deformation potentials could be determined, on the basis of models which considered the
intervalley electronphonon matrix elements to be a constant
characteristic of transitions between particular valleys
and independent of pressure, such as Conwells model
for intervalley scattering [9]. From the theoretical side,
semiempirical pseudopotential [10], and, later, ab initio
calculations [11, 12] demonstrated limitations of such
models, showing that the electronphonon matrix elements
change significantly over the Brillouin zone, even within
one valley, depending on the wavevector of initial and
final electronic states. In some cases, the effect of the
dispersion of electronphonon matrix elements can be
spectacular, leading to order-of-magnitude changes of
the calculated lifetimes and broadenings of the electronic
states, with respect to simple models where the dispersion
of the electronphonon matrix elements is neglected [13].
Ab initio calculations thus provide a means to reexamine the
commonly used approximations and models for the electronphonon coupling in semiconductors. In this work, we
examine the question of pressure and strain dependence of
the intervalley electronphonon matrix elements in the
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Phys. Status Solidi B 250, No. 4 (2013)

717

lowest conduction band, on the examples of Si, Ge, GaAs and

GaP semiconductors. We study both individual transitions
and average values in strained and hydrostatically compressed silicon. We provide general conclusions relatively to
the dependence on hydrostatic pressure of the intervalley
electronphonon matrix elements.
2 Computational method In this work, we use the
density functional theory and local density approximation to
describe atomic structure and electronic properties of GaAs,
GaP, Si and Ge, as in works [1214]. Norm-conserving
pseudopotentials were used. The details about the description of the atomic structure and the topology of the
conduction band within the approximation used, as well as
comparisons with experiments, can be found in work [12] for
GaAs and GaP, in work [13] for Si and in work [14] for Ge.
To describe phonons and the electronphonon matrix
elements, we use the density functional perturbation theory
[15]. In previous works, we have shown that our approach is
reliable and can be used to describe intervalley scattering in
semiconductors. The intervalley deformation potential,
Dlk;k
q , is a quantity proportional to the modulus of the
electron phonon matrix element:

Dlk;k
q

s

2Mvlq   l 


hck DVq ck
q i:

h


(1)

Here, DVql is the phonon-induced variation of the selfconsistent Kohn-Sham potential, for a phonon of mode l
with wave-vector q. ck and ck
q are initial and final Kohn
Sham electronic eigenstates, M is the mass of the unit cell,
and vlq is the phonon frequency. Plus and minus signs
correspond, respectively, to phonon emission or absorption.
In this work, we concentrate on the effects of hydrostatic
pressure and strain on intervalley electronphonon matrix
elements. The intervalley scattering rate Wk for a given
initial electronic state, however, is determined both by the
intervalley deformation potentials and by the density of final
electronic states via Fermis golden rule [12]:
Wk


p X 2nlq 1  l 2 
Dk;k
q  d ek
q  ek hvlq :
l
MN ql
vq
(2)

Here, N is the number of unit cells in the crystal, nlq is the

Boltzmann occupation number of the phonon (q, l), ek is the
KohnSham eigenenergy of the initial electronic state, and
ekWq is the energy of the final electronic state. The effective
intervalley deformation potentials can be obtained from
the intervalley scattering rate in Eq. (2), if one divides it by
the density of final electronic states allowed by energy and
momentum conservation laws.
As one can see from Eq. (2), final electronic states are
determined by both energy and momentum conservation
laws. Thus, the topology of the conduction band influences
the intervalley scattering rate Wk both via the density of
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available final states, that is the dispersion of the energy

levels , and via the q dependence of the deformation
potential. It is well known that the topology of the conduction
band in semiconductors depends strongly on pressure and
strain. In this work, we will not discuss the effect of
hydrostatic pressure on the dispersion of conduction energy
levels, nor on phonon frequencies of the semiconductors
under study. Such information can be found elsewhere [3, 4,
13, 16]. The effect of strain on the conduction energy band of
silicon will be discussed only very briefly. We followed the
method described in Ref. [17] to apply biaxial tensile strain
in our calculations on silicon (see also panels ac of the Fig. 1
of Ref. [17]). Strong q dependence (dispersion) of the
deformation potentials was demonstrated in previous works
[10, 12, 13]. In present work, the accent is made on the
pressure dependence of a single electronphonon matrix
element with fixed initial and final electronic states.
3 Results
3.1 Effect of a hydrostatic pressure First, we
study the dependence on a hydrostatic pressure of the
individual transitions between conduction band minima in
the first conduction band of GaAs, GaP, Si and Ge. For GaAs
and GaP, we consider scattering from G to the X or L points
of the Brillouin zone, as well as scattering between two
X points equivalent by symmetry, or between two L points.
Scattering channels which are allowed by symmetry
selection rules are denoted as TA (transverse acoustic), LA
(longitudinal acoustic), LO (longitudinal optical) and TO
(transverse optical), according to the phonon involved in the
transition. For Si and Ge, the first and second conduction
bands are degenerate at the X point, and the valley minimum
lies close to the X point in the D direction. We will denote the
position of this minimum as the point D. For Si and Ge,
we considered G to L, G to D, and D to D transitions. There
exist two types of D to D phonon-assisted intervalley
transitions: transitions between the opposite valleys, or
g-processes, and transitions between neighbouring valleys, or
f-processes [18]. We considered a pressure range of 8 GPa, in
order to avoid structural phase transitions which occur under
pressure at 9.7 GPa in Ge [4, 19], and at 10 GPa in Si [20].
The results for the hydrostatic pressure effect on
the deformation potentials for transitions between highsymmetry points are presented in Table 1. Application of a
hydrostatic pressure does not affect the symmetry selection
rules for electronphonon scattering [21], so that the number
of scattering channels remains the same.
It should be noted that in Ref. [16], we have already
studied the pressure dependence of the G ! X deformation
potential in GaAs. We found that its pressure dependence for
the first conduction band of GaAs is negligible. In present
work we generalize this finding.
For most of the transitions studied in all of the four
materials in Table 1, the pressure dependence of the
intervalley deformation potential was found to be weak
within the pressure range under study. Indeed, the change in
the absolute value of the deformation potential does not
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J. Sjakste et al.: Electronphonon coupling under pressure and strain

Table 1 Effect of a hydrostatic pressure on the deformation

potentials for transitions between high-symmetry points in the
conduction band.
)
)
transition
D (eV/A
D (eV/A
D change (%)

GaAs
G ! X, LO
G ! L, LO
G ! L, LA
X ! X, LO
L ! L, LO
L ! L, LA
GaP
G ! X, LA
G ! L, LO
G ! L, LA
X ! X, LA
L ! L, LO
L ! L, LA
Ge
G ! D, LO
G ! L, LA
D ! D, LOg
D ! D, LOf
D ! D, TOf
L ! L, LO/LA
Si
G ! D, TA1,2
G ! D, LA
G ! D, TO1,2
G ! L, LA
G ! L, TO1,2
D ! D, LOg
D ! D, LOf
D ! D, TOf
L ! L, LO/LA

0 GPa

8 GPa

8 GPa range

4.2
2.2
3.6
7.5
0.2
1.6

4.2
2.2
3.6
8.0
0.2
1.6

<1%
3%
<1%
7%
10%
5%

3.5
0.6
3.5
6.7
0.2
2.1

3.6
0.3
3.5
7.0
0.2
2.0

3%
50%
<1%
4%
4%
5%

2.5
4.0
5.5
2.6
5.1
0.8

2.3
4.0
5.5
3.0
5.2
0.9

8%
1%
<1%
15%
2%
12%

0.4
5.2
5.5
5.7
2.4
4.7
2.5
4.5
0.3

0.5
5.0
5.4
5.2
2.6
4.6
2.7
4.4
0.1

20%
3%
2%
9%
8%
2%
8%
2%
67%

exceed 15% between ambient pressure and a pressure as high

as 8 GPa. This rule does not hold for the deformation
1, i.e.
potentials with an absolute value smaller than 1 eV A
weak scattering channels. Considering the absolute changes
in the deformation potentials however, one can notice that
1. As can be
the latter never change by more than 0.5 eV A
seen from Table 1, we considered a wide range of pressure,
materials and transitions. A general conclusion can thus be
drawn that the electronphonon matrix elements depend
very weakly on hydrostatic pressure. This study validates the
approximation of pressure-independent deformations potentials, which can be safely used for the interpretation of
experiments where the direct exciton linewidth is measured
[24]. This conclusion is expected to be valid also for
transport experiments. We have to point out however, that in
case one considers a phenomenon in which, for some reason,
weak scattering channels become very important, caution is
needed and pressure-dependence of the electronphonon
matrix elements should be taken into account, or at least
examined before they are neglected.
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

We also point out that although we have shown here

that the individual electronphonon matrix elements do
not directly depend on pressure, the effective deformation
potentials, averaged over transitions allowed by the
conservation laws (see Eq. (2)), may still depend on pressure,
as the topology of the conduction band changes under
pressure, and matrix elements which contribute to the
average value at different pressures correspond to different
initial and final electronic states [16].
3.2 Effect of a biaxial strain In this section, we
consider the effect of a 1% biaxial tensile strain on the
intervalley deformation potentials in silicon. Under this
type of strain, the sixfold symmetry of the D valley is lifted,
resulting in valleys with twofold symmetry (D2) and valleys
with fourfold symmetry (D4). In the tensile strain case, D2
valleys are lower in energy with respect to D4 ones. The
lowest conduction band at G point is not degenerate in
strained silicon, at variance with the triply degenerate lowest
conduction band in unstrained silicon at the G point. Our
results for the biaxially strained silicon (tensile strain case)
conduction band are in agreement with previous studies [17].
If now one considers electronphonon selection rules in
strained silicon, additional scattering channels are present
relatively to the unstrained case. In order to make the
study of the strain effect on the deformation potentials
more straightforward, instead of comparing strained and
unstrained cases, we will compare the case of a 0.1% strain,
which can be considered as the very small strain case, and the
case of a 1% strain. In Table 2, we report a comparison
between intervalley deformation potentials in silicon for
0.1% strain and 1% strain. For D to D transitions, we limited
this study to g-processes. Although we still find that most
deformation potentials change weakly with strain, the results
presented in Table 2 are different from the effect of a
hydrostatic pressure reported in the previous section. Indeed,
for several scattering channels, deformation potentials
strongly depend on strain. In the case of the D2 to D2
Table 2 Effect of a biaxial tensile strain on the deformation
potentials of Si for transitions between high-symmetry points in
the conduction band.
)
)
transition
D (eV/A
D (eV/A
D change (%)

G ! D2, TA
G ! D2, TO
G ! D4, TA
G ! D4, LA
G ! D4, TO
G ! L, LA
G ! L, TO
D2 ! D2, LAg
D2 ! D2, LOg
D4 ! D4, TOg
D4 ! D4, LOg

0.1% strain

1% t. strain

0.5
5.4
0.5
3.4
4.0
4.6
1.5
0.1
4.7
0.3
4.7

0.2
6.2
0.5
3.1
4.2
4.6
1.5
1.2
4.8
1.3
4.5

60%
15%
11%
10%
5%
<1%
1%
1100%
2%
300%
4%

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Phys. Status Solidi B 250, No. 4 (2013)

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scattering with LAg phonon, we observe a strong dependence

on strain, as this weak scattering channel becomes a strong
scattering channel upon 1% strain. The same type of
behaviour is observed for the D4 to D4 scattering with TOg
phonon. In both cases, the strong strain-dependence
concerns additional scattering channels, i.e. scattering
channels which appeared because some symmetry selection
rules were lifted with respect to the completely unstrained
silicon case.
This study is limited to silicon, and to only one type of
strain, and the results cannot be generalized. From Table 2
we conclude that, deformation potentials for additional
scattering channels depend very strongly on strain. The
question we will address in the next section is, whether this
dependence on strain of the matrix elements for transitions
between high-symmetry points can influence transport
properties of materials.
3.3 Parameters for transport simulations: Si In
this section, we examine the findings of previous two
sections from the point of view of transport properties.
Indeed, instead of matrix elements for individual transitions
between high-symmetry points, calculations of transport
properties require effective deformation potentials, i.e.
quantities averaged over many transitions [11]. In the case
of silicon, D to D transitions have to be taken into account in
mobility calculations. In Ref. [22], we combined our data for
the average deformation potentials with the Boltzmann
transport equation. In present work, we will examine how
these parameters are affected by hydrostatic pressure and by
strain.
In Table 3, we present the average deformation
potentials for g-type D to D transitions in zero-strain zeropressure silicon, silicon at 8 GPa hydrostatic pressure, and
1% biaxially strained silicon (tensile case). The transitions
were averaged over 125 initial and 125 final states close to
the minimum of the D valley. In the case of strained silicon,
both D2 to D2 and D4 to D4 g-type transitions were considered.
In analogy with our previous work [22], the data of Table 3
can be directly used in calculations of transport properties of
silicon. In Ref. [22] however, deformation potentials were
averaged only over final states, which explains the slight
difference between data presented in the first column of
Table 3 and those reported in Table 1 of Ref. [22].
Table 3 Effect of a hydrostatic pressure and of a biaxial tensile
) for g-prostrain on effective deformation potentials Dav (eV/A
cesses in Si. Superscripts 0th and 1st denote zero-order and firstorder transitions, respectively (see text).
scattering
channel

TA
LA
TO
LO

equil.

8 GPa

1% strain

1% strain

D!D

D!D

D2 ! D2

D4 ! D4

0.81st
1.71st
1.21st
4.00th

0.91st
1.91st
1.41st
3.80th

0.81st
1.80th
2.91st
3.20th

0.81st
1.61st
1.80th
3.80th

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As one can see from Table 1, only the LO scattering

channel is allowed by symmetry selection rules for gscattering between two conduction band minima in
unstrained Si. The contributions of other scattering channels
presented in the first column of Table 3 are due to the strong
dispersion of the electronphonon matrix elements close to
the conduction band minima. The scattering channels which
are allowed by symmetry selection rules for transitions
between high-symmetry points are called zero-order channels, the ones which are forbidden are called first-order
channels, see Refs. [13, 22, 23].
As one can see from Table 3, second column, our conclusions about the hydrostatic pressure effect of Section 3.1,
where individual transitions were studied, are confirmed by the
study of 15 625 transitions. Indeed, the average deformation
potentials at 8 GPa are very close to zero-pressure ones.
Now, we examine the effect of tensile strain on the
average deformation potentials (Table 3, third and fourth
columns). Now the scattering channels which are allowed by
symmetry selection rules for transitions between highsymmetry points under infinitesimal strain are called zeroorder channels. Surprisingly, average deformation potentials
for g-scattering in strained crystal are close to the ones in
unstrained crystal. The most significant change concerns the
TO scattering channel in the case of D2 to D2 transitions. In
this case, the average deformation potential in strained
silicon is 2.4 times larger than the unstrained one. This result
means that although strain can cause significant changes in
some individual electronphonon matrix elements at high
symmetry points, these changes are mostly smoothened
when many transitions are taken into account. Our results are
thus in overall agreement with the statement made in recent
work [24], that the strain dependence of the intervalley
scattering parameters does not influence the electronic
mobility. The work [24], however, does not provide data
that could be directly compared to the results in our Table 3.
Nevertheless, the significant change in the TO average
deformation potential for D2 to D2 transitions (Table 3,
third column) means that the dependence of the intervalley
deformation potentials on strain can not be neglected
without a case-by-case examination, and it is preferable to
take this dependence into account explicitly in transport
calculations.
3.4 Discussion As we have shown in previous sections, intervalley deformation potentials in IV and IIIV
semiconductors do not heavily depend on hydrostatic
pressure. This result explains in part why simple models
such as Conwells one [9] are able to describe the change in
intervalley scattering rate as a function of pressure, as it was
done in Refs. [3, 4] and in many other ones. Our previous
works, and the works of Ref. [10], have shown, however, that
deformation potentials depend strongly on the wavevector of
the initial and final electronic states (k and q in Eqs. (1) and (2)).
We thus conclude here that in the case of experiments under
hydrostatic pressure, such as measurements of the direct
exciton linewidth, or transport experiments, the change in the
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J. Sjakste et al.: Electronphonon coupling under pressure and strain

intervalley scattering rate can be attributed uniquely to

the change of the conduction band under pressure (change
under pressure of the relative valley positions and of valley
shape), and to the dispersion of the intervalley deformation
potentials. In the case of strained silicon, we do find
additional dependence of the intervalley deformation
potentials on strain. Nevertheless, spectacular changes of
the mobility in silicon [17, 24, 25] or in Ge [26] under some
types of strain should still be mainly attributed to the changes
in crystal symmetry, relative valley positions, and effective
masses in the lowest conduction band, and to changes in
other scattering processes [27, 28], as the effect of strain
on the average intervalley deformation potentials is only
moderate.
4 Conclusions In conclusion, we have examined the
hydrostatic pressure dependence of a wide range of
intervalley transitions in group IV and IIIV semiconductors, as well as the hydrostatic pressure dependence of the
average parameters for transport calculations in silicon.
Biaxial strain dependence of the intervalley deformation
potentials was studied in silicon. In the case of a hydrostatic
pressure, we draw the general conclusion that hydrostatic
pressure dependence of the intervalley electronphonon
matrix elements can be safely neglected in the interpretation
of most commonly studied phenomena. In contrast, the case
of a biaxial strain in silicon shows that strain-dependence
should be taken into account in calculations of the intervalley
electronphonon matrix elements. Nevertheless, we predict
that this strain-dependence should have only a moderate
influence on the final characteristics of materials, such as
mobility.
Acknowledgements This work has been performed under
the auspices of the Laboratoire dExcellence en Nanosciences et
Nanotechnologies LABEX NanoSaclay. It has been supported by
the French ANR (project PNANO ACCATTONE). Results have
been obtained with the Quantum Espresso package [15]. We also
acknowledge support from the DGA. Computer time has been
granted by CEA/DSM (project p93) and GENCI (project 2210).
H. Jani acknowledges support from the Ecole Polytechnique
(Direction des Relations Exterieures). J. Sjakste acknowledges
discussions with F. Murphy-Armando.

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